U.S. patent application number 15/539225 was filed with the patent office on 2018-01-25 for polyethylene compositions with improved optical properties.
This patent application is currently assigned to Dow Global Technologies LLC. The applicant listed for this patent is Dow Global Technologies LLC. Invention is credited to Seda Aksel, Selim Bensason, Martin K. Hill, Hans-Werner Schmidt, Paul Smith.
Application Number | 20180022894 15/539225 |
Document ID | / |
Family ID | 52134083 |
Filed Date | 2018-01-25 |
United States Patent
Application |
20180022894 |
Kind Code |
A1 |
Hill; Martin K. ; et
al. |
January 25, 2018 |
POLYETHYLENE COMPOSITIONS WITH IMPROVED OPTICAL PROPERTIES
Abstract
Embodiments of a polyethylene composition comprise at least 50%
by wt. of at least one polyethylene polymer; and 0.001 to 2% by wt.
of bisamide nucleating agent utilized to reduce haze within the
polyethylene composition.
Inventors: |
Hill; Martin K.; (Tarragona,
ES) ; Bensason; Selim; (Horgen, CH) ; Schmidt;
Hans-Werner; (Bayreuth, DE) ; Smith; Paul;
(Zurich, CH) ; Aksel; Seda; (Zurich, CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Global Technologies LLC |
Midland |
MI |
US |
|
|
Assignee: |
Dow Global Technologies LLC
Midland
MI
|
Family ID: |
52134083 |
Appl. No.: |
15/539225 |
Filed: |
September 17, 2015 |
PCT Filed: |
September 17, 2015 |
PCT NO: |
PCT/US2015/050688 |
371 Date: |
June 23, 2017 |
Current U.S.
Class: |
524/229 |
Current CPC
Class: |
C07C 2601/14 20170501;
C08L 2205/24 20130101; C07C 2601/16 20170501; C08L 2203/16
20130101; C07C 233/65 20130101; C08J 5/18 20130101; C07C 233/57
20130101; C08K 5/20 20130101; C08L 2201/10 20130101; C08J 2323/06
20130101; C08L 23/06 20130101; C08K 5/20 20130101; C08L 23/08
20130101 |
International
Class: |
C08K 5/20 20060101
C08K005/20; C07C 233/65 20060101 C07C233/65; C07C 233/57 20060101
C07C233/57; C08J 5/18 20060101 C08J005/18; C08L 23/06 20060101
C08L023/06 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 23, 2014 |
EP |
14382561.0 |
Claims
1. A polyethylene composition comprising: at least 50% by wt. of at
least one polyethylene polymer chosen from a linear low density
polyethylene polymer (LLDPE), a low density polyethylene polymer
(LDPE), a high density polyethylene polymer (HDPE), or combinations
thereof; and 0.001 to 2% by wt nucleating agent comprising a
structure of formulas (I), (II), or (III): ##STR00030## wherein R1
and R2 comprise the same or different moieties chosen from:
C.sub.1-C.sub.20 alkyl unsubstituted or substituted by one or more
hydroxy; C.sub.4-C.sub.20 alkenyl unsubstituted or substituted by
one or more hydroxy; C.sub.2-C.sub.20 alkyl interrupted by oxygen
or sulfur; C.sub.3-C.sub.12 cycloalkyl unsubstituted or substituted
by one or more C.sub.1-C.sub.20 alkyl; (C3-C.sub.12
cycloalkyl)-C.sub.1-C.sub.10 alkyl unsubstituted or substituted by
one or more C.sub.1-C.sub.20 alkyl; bis[C.sub.3-C.sub.12
cycloalkyl]-C.sub.1-C.sub.10 alkyl unsubstituted or substituted by
one or more C.sub.1-C.sub.20 alkyl; a bicyclic or tricyclic
hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or
substituted by one or more C.sub.1-C.sub.20 alkyl; phenyl
unsubstituted or substituted by one or more radicals selected from
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20
alkylamino, di(C.sub.1-C.sub.20 alkyl)amino, hydroxy and nitro;
phenyl-C.sub.1-C.sub.20 alkyl unsubstituted or substituted by one
or more radicals selected from C.sub.1-C.sub.20 alkyl, C.sub.3-C12
cycloalkyl, phenyl, C.sub.1-C.sub.20 alkoxy and hydroxy;
phenylethenyl unsubstituted or substituted by one or more
C.sub.1-C.sub.20 alkyl; biphenyl-(C.sub.1-C.sub.10 alkyl)
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
naphthyl unsubstituted or substituted by one or more
C.sub.1-C.sub.20 alkyl; naphthyl-C.sub.1-C.sub.20 alkyl
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
naphthoxymethyl unsubstituted or substituted by one or more
C.sub.1-C.sub.2 alkyl; biphenylenyl, flourenyl, anthryl; a
5-to-6-membered heterocylic radical unsubstituted or substituted by
one or more C.sub.1-C.sub.20 alkyl; a C.sub.1-C.sub.20 hydrocarbon
radical containing one or more halogen; or tri(C.sub.1-C.sub.10
alkyl)silyl(C.sub.1-C.sub.10 alkyl); wherein, when the polyethylene
composition is used to form an article, the article has a haze
value reduction of at least 15% when compared to an article having
the same polyethylene polymer but free of the nucleating agent.
2. The polyethylene composition of claim 1 wherein the polyethylene
polymer is copolymer of ethylene with alpha-olefin copolymers, an
ethylene homopolymer or combinations thereof.
3. (canceled)
4. The polyethylene composition according to claim 1 wherein the
polyethylene composition has a melt index (I.sub.2).ltoreq.50 g/10
min, wherein I.sub.2 is measured according to ASTM D1238 at
190.degree. C. and 2.16 kg load, and a density about 0.855 to about
0.970 g/cm.sup.3.
5. The polyethylene composition according to claim 1 wherein the
polyolefin resin comprises 0.01-0.5% by wt of the nucleating
agent.
6. The polyethylene composition according to claim 1 wherein R1,
R2, or both are ##STR00031## wherein R3 is a direct bond, or a
C.sub.1-C.sub.6 alkyl.
7. The polyethylene composition according to claim 1 wherein R1, R2
or both are ##STR00032## wherein R3 is a direct bond, or a
C.sub.1-C.sub.6 alkyl.
8. The polyethylene composition according to claim 1 wherein R1,
R2, or both are ##STR00033## wherein R3 is a direct bond, or a
C.sub.1-C.sub.6 alkyl.
9. The polyethylene composition according to claim 1 wherein R1,
R2, or both are ##STR00034## wherein R3 is a direct bond, or a
C.sub.1-C.sub.6 alkyl.
10. The polyethylene composition according to claim 1 wherein R1,
R2, or both are a C.sub.1-C.sub.6 alkyl.
11. The polyethylene composition according to claim 1 wherein the
polyethylene composition comprises greater than about 60% by wt.,
or preferably greater than about 80% by wt. polyethylene
polymer.
12. An article produced from the polyethylene composition of any of
the preceding claims, wherein the article has a haze value
reduction of at least 20% when compared to an article having the
same polyethylene polymer but free of the nucleating agent.
13. The article of claim 12 wherein the article is chosen from a
blown film, a cast film, a molded article, a melt-spun fiber, or an
extruded article, wherein the extruded article is chosen form
sheets, pipes, or tubes.
14. (canceled)
15. The polyethylene according to claim 1 wherein said polyethylene
composition has a density of about 0.910 to about 0.940
g/cm.sup.3.
16. The polyethylene according to claim 1 wherein the polyethylene
composition is substantially free of polypropylene.
17. The polyethylene according to claim 1 wherein polyethylene
composition comprises 0.5% by weight to 15% by weight
polypropylene.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application hereby claims the benefit of EPO
Patent Application No. 14382561.0 filed Dec. 23, 2014.
FIELD
[0002] Embodiments of the present disclosure relate to a
polyethylene composition, more particularly, a polyethylene
composition yielding improved optical performance via inclusion of
a bisamide nucleating agent.
BACKGROUND
[0003] Polyethylene compositions and resins are utilized in various
applications and articles, for example, in the production of molded
articles, blown films, and various other articles. Additives used
for increasing the rate of nucleation during crystallization of
semi-crystalline polymers are termed nucleators or nucleating
agents. The addition of nucleating agents typically increases the
overall rate of crystallization, and crystallization temperature of
the polymers. This generally translates to faster solidification,
and may be used to reduce the cycle time in processes like
injection molding. Nucleators may also influence other properties,
such as stiffness, toughness, haze, gloss, permeability and
shrinkage. Nucleators that improve optical properties like haze and
clarity are termed clarifiers. Various organic and/or inorganic
additives may serve as nucleators, such as benzoic acids, talc,
pigments, sorbitols, phosphate ester derivatives, and other
polymeric species.
[0004] Derivatives of dibenzylidene sorbitol are well known
clarifiers for polypropylene resins and films. The use of
clarifiers in polyethylene resins and films is not common, due to
much higher rates of crystallization in polyethylene compared to
polypropylene, which makes haze reduction and the improvement of
optical properties more challenging for polyethylene films and
resins. Regarding the use of clarifiers, there is no known
correlation between effective haze reduction for polypropylene
compositions and effective haze reduction for polyethylene
compositions.
[0005] Accordingly, there may be a continual need for nucleating
agents which increase the rate of crystallization in polyethylene
compositions while also reducing the haze and thereby improve the
optical properties.
SUMMARY
[0006] Embodiments of the present invention are directed to
polyethylene compositions having bisamide nucleating agents which
reduce haze in the polyethylene compositions while also increasing
the rate of crystallization in the polyethylene composition.
[0007] According to one embodiment, a polyethylene composition is
provided comprising: at least 50% by wt. of at least one
polyethylene polymer; and 0.001 to 2% by wt. nucleating agent
comprising a structure of formulas (I), (II), or (III):
##STR00001##
wherein R1 and R2 comprise the same or different moieties chosen
from: C.sub.1-C.sub.20 alkyl unsubstituted or substituted by one or
more hydroxy; C.sub.4-C.sub.20 alkenyl unsubstituted or substituted
by one or more hydroxy; C.sub.2-C.sub.20 alkyl interrupted by
oxygen or sulfur; C.sub.3-C.sub.12 cycloalkyl unsubstituted or
substituted by one or more C.sub.1-C.sub.20 alkyl; (C3-C.sub.12
cycloalkyl)-C.sub.1-C.sub.10 alkyl unsubstituted or substituted by
one or more C.sub.1-C.sub.20 alkyl; bis[C.sub.3-C.sub.12
cycloalkyl]-C.sub.1-C.sub.10 alkyl unsubstituted or substituted by
one or more C.sub.1-C.sub.20 alkyl; a bicyclic or tricyclic
hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or
substituted by one or more C.sub.1-C.sub.20 alkyl; phenyl
unsubstituted or substituted by one or more radicals selected from
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, C.sub.1-C.sub.20
alkylamino, di(C.sub.1-C.sub.20 alkyl)amino, hydroxy and nitro;
phenyl-C.sub.1-C.sub.20 alkyl unsubstituted or substituted by one
or more radicals selected from C.sub.1-C.sub.20 alkyl, C.sub.3-C12
cycloalkyl, phenyl, C.sub.1-C.sub.20 alkoxy and hydroxy;
phenylethenyl unsubstituted or substituted by one or more
C.sub.1-C.sub.20 alkyl; biphenyl-(C.sub.1-C.sub.10 alkyl)
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
naphthyl unsubstituted or substituted by one or more
C.sub.1-C.sub.20 alkyl; naphthyl-C.sub.1-C.sub.20 alkyl
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
naphthoxymethyl unsubstituted or substituted by one or more
C.sub.1-C.sub.2 alkyl; biphenylenyl, flourenyl, anthryl; a
5-to-6-membered heterocylic radical unsubstituted or substituted by
one or more C.sub.1-C.sub.20 alkyl; a C.sub.1-C.sub.20 hydrocarbon
radical containing one or more halogen; or tri(C.sub.1-C.sub.10
alkyl)silyl(C.sub.1-C.sub.10 alkyl).
DETAILED DESCRIPTION
[0008] Embodiments of the present disclosure are directed to
polyethylene compositions comprising haze reducing bisamide
nucleating agents. Because of the inclusion of bisamide nucleating
agents, the present compositions demonstrate high transmittance,
high clarity, and low haze.
[0009] In specific embodiments, the polyethylene compositions may
comprise at least 50% by wt. of at least one polyethylene polymer;
and 0.001 to 2% by wt nucleating agent. The polyethylene
compositions may comprise a structure of formulas (I), (II), or
(III):
##STR00002##
[0010] wherein R1 and R2 comprise the same or different moieties
chosen from: C.sub.1-C.sub.20 alkyl unsubstituted or substituted by
one or more hydroxy; C.sub.4-C.sub.20 alkenyl unsubstituted or
substituted by one or more hydroxy; C.sub.2-C.sub.20 alkyl
interrupted by oxygen or sulfur; C.sub.3-C.sub.12 cycloalkyl
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
(C3-C.sub.12 cycloalkyl)-C.sub.1-C.sub.10 alkyl unsubstituted or
substituted by one or more C.sub.1-C.sub.20 alkyl;
bis[C.sub.3-C.sub.12 cycloalkyl]-C.sub.1-C.sub.10 alkyl
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon
atoms unsubstituted or substituted by one or more C.sub.1-C.sub.20
alkyl; phenyl unsubstituted or substituted by one or more radicals
selected from C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy,
C.sub.1-C.sub.20 alkylamino, di(C.sub.1-C.sub.20 alkyl)amino,
hydroxy and nitro; phenyl-C.sub.1-C.sub.20 alkyl unsubstituted or
substituted by one or more radicals selected from C.sub.1-C.sub.20
alkyl, C.sub.3-C12 cycloalkyl, phenyl, C.sub.1-C.sub.20 alkoxy and
hydroxy; phenylethenyl unsubstituted or substituted by one or more
C.sub.1-C.sub.20 alkyl; biphenyl-(C.sub.1-C.sub.10 alkyl)
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
naphthyl unsubstituted or substituted by one or more
C.sub.1-C.sub.20 alkyl; naphthyl-C.sub.1-C.sub.20 alkyl
unsubstituted or substituted by one or more C.sub.1-C.sub.20 alkyl;
naphthoxymethyl unsubstituted or substituted by one or more
C.sub.1-C.sub.2 alkyl; biphenylenyl, flourenyl, anthryl; a
5-to-6-membered heterocylic radical unsubstituted or substituted by
one or more C.sub.1-C.sub.20 alkyl; a C.sub.1-C.sub.20 hydrocarbon
radical containing one or more halogen; or tri(C.sub.1-C.sub.10
alkyl)silyl(C.sub.1-C.sub.10 alkyl);
[0011] In one embodiment, the R1, R2, or both of the nucleating
agent is
##STR00003##
wherein R3 is a direct bond, or a C.sub.1-C.sub.6 alkyl, or a
C.sub.1-C.sub.3 alkyl.
[0012] In another embodiment, the R1, R2 or both of the nucleating
agents are
##STR00004##
wherein R3 is a direct bond, or a C.sub.1-C.sub.6 alkyl, or a
C.sub.1-C.sub.3 alkyl.
[0013] In a further embodiment, the R1, R2 or both of the
nucleating agents are
##STR00005##
wherein R3 is a direct bond, or a C.sub.1-C.sub.6 alkyl, or a
C.sub.1-C.sub.3 alkyl.
[0014] In yet another embodiment, the R1, R2, or both of the
nucleating agents are
##STR00006##
wherein R3 is a direct bond, or a C.sub.1-C.sub.6 alkyl, or a
C.sub.1-C.sub.3 alkyl.
[0015] In yet another embodiment, the R1, R2, or both of the
nucleating agents are a C.sub.1-C.sub.6 alkyl, or a C.sub.1-C.sub.3
alkyl.
[0016] As used herein, "polyethylene composition" means any
formulation comprising polyethylene polymer solely or with
additional components, such as an additional polymer. As used
herein, "polyethylene polymer" refers to a polymer made of 100%
ethylene-monomer units, i.e., a homopolymer, or to copolymers
produced with other monomeric moieties such as .alpha.-olefins,
e.g. propylene, 1-butene, 1-pentene, 1-hexene or 1-octene, etc.
Various polyethylene polymers are contemplated as suitable. For
example and not by way of limitation, the polyethylene polymers may
include a high density polyethylene (HDPE), high density and high
molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), very low density polyethylene
(VLDPE), and ultra low density polyethylene (ULDPE), or mixtures
thereof.
[0017] In one or more embodiments, the polyethylene polymer may
have a melt index (12) .ltoreq.50 g/10 min, wherein 12 is measured
according to ASTM D1238 at 190.degree. C. and 2.16 kg load, and a
density about 0.855 to about 0.970 g/cm.sup.3. In other
embodiments, the 12 may be .ltoreq.25 g/10 min, or .ltoreq.10 g/10
min. In further embodiments, the density may be 0.900-0.955
g/cm.sup.3, or 0.910-0.940 g/cm.sup.3.
[0018] For example and not by way of limitation, suitable
commercial examples of the LLDPE may include one or more of
DOWLEX.RTM. 2045 G, DOWLEX.RTM. 2552 E, or TUFLIN.TM. HS-7028 which
are available from The Dow Chemical Company, Midland Mich. Other
compositions having either homogeneous or heterogeneous short chain
branching distributions, or compositions with broad or narrow
molecular weight distributions are considered suitable. Various
other resins, such as EXCEED.TM. from Exxon-Mobil, or EVOLUE.TM.
from Prime Polymer Co., Ltd. are also contemplated.
[0019] The polyethylene composition comprises greater than about
50% by wt., or greater than about 60% by wt., or greater than about
70% by wt., or greater than about 80% by wt., or greater than about
90% by wt. of polyethylene polymer. Additionally, the polyethylene
composition may comprise about 0.001 to about 2% by wt., or about
0.001 to about 1% by wt., or about 0.005 to about 1% by wt, or
about 0.01 to about 0.5% by wt., or about 0.1 to about 0.5% by wt.,
or 0.01 to about 0.1 wt % of the nucleating agent. Without being
bound by theory, haze reduction may vary depending on which R (R1
and R2) groups are utilized in structures I, II, and III.
Specifically, the various R groups may have various solubilities
inside the polyethylene composition. Unsolubilized nucleating agent
may increase haze, thus selecting a concentration which minimizes
the amount of unsolubilized nucleating agent may be beneficial.
[0020] In one embodiment, the polyethylene composition is
substantially free of polypropylene. In additional embodiments, it
is contemplated to include further polymers for blending with the
polyethylene polymer. For example, it is contemplated to include a
blend of multiple polyethylene polymers. Moreover, it is also
contemplated to blend the polyethylene polymers with a
polypropylene polymer. For example, it is contemplated that a
second polymer may be included in amounts from about 0.5 to about
45% by wt., or about 1 to about 25% by wt., or about 5 to about 15%
by wt.
[0021] The polyethylene composition may be formed into various
articles. For example, the article may be a blown film, a cast
film, or a molded article (for example, injection molding, or
rotational molding). The articles may be extruded or formed into
various extruded profiles such as sheets, pipes, or tubes.
Moreover, in further embodiments, the articles may be melt-spun
fibers. Upon inclusion of the present bisamide nucleating agents,
the article may achieve a haze value reduction of at least 15% when
compared to an article having the same polyethylene polymer but
without the bisamide nucleating agent. In further embodiment, the
article may achieve a haze reduction of at least 20%, or at least
25%, or at least 30%, or at least 35%, or at least 40% when
compared to an article having the same polyethylene polymer but
without the bisamide nucleating agent. Various dimensions and
thicknesses are contemplated for the polyethylene articles. The
articles may comprise a thickness of 0.001 mm to about 5 mm, or
about 0.5 mm to about 2.5 mm, or about 0.5 mm to about 1.5 mm.
[0022] Various procedures are contemplated for producing the
present composition. For example and not by way of limitation,
these procedures may include standard procedures such as mixing the
prescribed components in a conventional mixer and/or melting,
kneading, and/or extruding the mixture.
[0023] Additional optional materials may be added to the
compositions of the present disclosure. For example, these
materials may include antioxidants, antibacterial agents,
ultraviolet absorbers, light stabilizers, neutralizers, antistatic
agents, antiblocking agents, flame retardants, lubricants, various
other processing aids and fillers, and the like and mixtures
thereof. Additional information on the optional materials is
provided in U.S. Pat. No. 7,790,793, which is incorporated by
reference herein in its entirety.
Examples
[0024] Part A: Preparation of Bisamide Nucleating Agents
[0025] The following lists exemplary bisamide structures and method
of making.
Example 1: Method of Making
N,N'-Dicyclohexyl-1,4-benzenedicarboxamide
##STR00007##
[0027] N-methylpyrrolidone (NMP) was stirred for 1 day over
CaH.sub.2 and finally distilled off. Triethylamine was treated in a
similar manner. Cyclohexylamine was stirred over KOH and distilled
off. 5.5 mL of cyclohexylamine, 0.1 g of anhydrous LiCl, and 25 mL
of triethylamine were dissolved in 100 mL of dry NMP under inert
atmosphere. 4.06 g of terephthaloyl chloride were added to the
solution and subsequently stirred for 2 h at 75.degree. C. Then the
solution was cooled to room temperature and poured into ice-water.
The precipitate was filtered off, washed several times with water.
The crude product was recrystallized from DMF, yielding 4.03 g of
N,N'-Dicyclohexyl-1,4-benzenedicarboxamide as white powder.
Example 2: N,N'-Bis(cyclohexylmethyl)-1,4-benzenedicarboxamide
##STR00008##
[0029] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. Tetrahydrofuran (THF) was refluxed for three
days over CaH.sub.2, distilled, refluxed for another three days
over potassium and finally distilled again. 3.75 mL of
cyclohexyanemethylamine, 0.1 g of anhydrous LiCl, and 15 mL of
triethylamine were dissolved in 150 mL of dry THF under inert
atmosphere and cooled to 0.degree. C. 2.66 g of terephthaloyl
chloride were added to the solution and subsequently refluxed for
12 h. Then the solution was cooled to room temperature and poured
into ice-water. The precipitate was filtered off, washed several
times with water. The crude product was recrystallized from DMSO,
yielding 4.25 g of
N,N'-Bis(cyclohexylmethyl)-1,4-benzenedicarboxamide as white
needles.
Example 3: N,N'-Bis(cyclohexylethyl)-1,4-benzenedicarboxamide
##STR00009##
[0031] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. THF was refluxed for three days over
CaH.sub.2, distilled, refluxed for another three days over
potassium and finally distilled again. 3.25 mL of
cyclohexyaneethylamine, 0.1 g of anhydrous LiCl, and 15 mL of
triethylamine were dissolved in 150 mL of dry THF under inert
atmosphere and cooled to 0.degree. C. 2.03 g of terephthaloyl
chloride were added to the solution and subsequently refluxed for
12 h. Then the solution was cooled to room temperature and poured
into ice-water. The precipitate was filtered off, washed several
times with water. The crude product was recrystallized from DMSO,
yielding 3.79 g of
N,N'-Bis(cyclohexylethyl)-1,4-benzenedicarboxamide as white
needles.
Example 4: N,N'-Bis(isopropyl)-1,4-benzenedicarboxamide
##STR00010##
[0033] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. THF was refluxed for three days over
CaH.sub.2, distilled, refluxed for another three days over
potassium and finally distilled again. 2.77 mL of isopropylamine,
0.1 g of anhydrous LiCl, and 15 mL of triethylamine were dissolved
in 100 mL of dry THF under inert atmosphere and cooled to 0.degree.
C. 3.00 g of terephthaloyl chloride were added to the solution and
subsequently refluxed for 12 h. Then the solution was cooled to
room temperature and poured into ice-water. The precipitate was
filtered off, washed several times with water. The crude product
was recrystallized from methanol, yielding 2.40 g of
N,N'-Bis(isopropyl)-1,4-benzenedicarboxamide as white crystals.
Example 5: N,N'-Bis(2-methylpropyl)-1,4-benzenedicarboxamide
##STR00011##
[0035] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. THF was refluxed for three days over
CaH.sub.2, distilled, refluxed for another three days over
potassium and finally distilled again. 3.26 mL of isobutylamine,
0.1 g of anhydrous LiCl, and 15 mL of triethylamine were dissolved
in 100 mL of dry THF under inert atmosphere and cooled to 0.degree.
C. 3.00 g of terephthaloyl chloride were added to the solution and
subsequently refluxed for 12 h. Then the solvent was evaporated,
the residue was dissolved in MeOH, and poured into ice-water. The
precipitate was filtered off, washed several times with water,
yielding 2.09 g of
N,N'-Bis(2-methylpropyl)-1,4-benzenedicarboxamide as white
powder.
Example 6: N,N'-Bis(2-methylbutyl)-1,4-benzenedicarboxamide
##STR00012##
[0037] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. THF was refluxed for three days over
CaH.sub.2, distilled, refluxed for another three days over
potassium and finally distilled again. 3.35 mL of
3-methylbutylamine, 0.1 g of anhydrous LiCl, and 15 mL of
triethylamine were dissolved in 100 mL of dry THF under inert
atmosphere and cooled to 0.degree. C. 2.66 g of terephthaloyl
chloride were added to the solution and subsequently refluxed for
12 h. Then the solution was cooled to room temperature and poured
into ice-water. The precipitate was filtered off, washed several
times with water. The crude product was recrystallized from DMSO,
yielding 2.98 g of N,N'-Bis(2-methylbutyl)-1,4-benzenedicarboxamide
as white powder.
Example 7: N,N'-Bis(tert-butyl)-1,4-benzenedicarboxamide
##STR00013##
[0039] NMP was stirred for 1 day over CaH.sub.2 and finally
distilled off. Triethylamine was treated in a similar manner. 5.04
mL of tert-butylamine, 0.1 g of anhydrous LiCl, and 25 mL of
triethylamine were dissolved in 100 mL of dry NMP under inert
atmosphere. 4.06 g of terephthaloyl chloride were added to the
solution and subsequently stirred for 2 h at 75.degree. C. Then the
solution was cooled to room temperature and poured into ice-water.
The precipitate was filtered off, washed several times with water.
The crude product was recrystallized from DMF, yielding 3.68 g of
N,N'-Bis(tert-butyl)-1,4-benzenedicarboxamide as whitish
needles.
Example 8:
N,N'-Bis(2,2-dimethylpropyl)-1,4-benzenedicarboxamide
##STR00014##
[0041] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. THF was refluxed for three days over
CaH.sub.2, distilled, refluxed for another three days over
potassium and finally distilled again. 3.17 mL of amylamine, 0.1 g
of anhydrous LiCl, and 12 mL of triethylamine were dissolved in 70
mL of dry THF under inert atmosphere and cooled to 0.degree. C.
2.50 g of terephthaloyl chloride were added to the solution and
subsequently refluxed for 12 h. Then the solvent was evaporated,
the residue was dissolved in MeOH, and poured into ice-water. The
precipitate was filtered off, washed several times with water and
hexane and dried in vacuum, yielding 3.23 g of
N,N'-Bis(2,2-dimethylpropyl)-1,4-benzenedicarboxamide as white
powder.
Example 9: N,N'-Bis(3,3-dimethylbutyl)-1,4-benzenedicarboxamide
##STR00015##
[0043] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. THF was refluxed for three days over
CaH.sub.2, distilled, refluxed for another three days over
potassium and finally distilled again. 1.33 mL of
3,3-dimethylbutylamine, 0.1 g of anhydrous LiCl, and 5 mL of
triethylamine were dissolved in 50 mL of dry THF under inert
atmosphere and cooled to 0.degree. C. 0.91 g of terephthaloyl
chloride were added to the solution and subsequently refluxed for
12 h. Then the solvent was evaporated, the residue was dissolved in
MeOH, and poured into water. The precipitate was filtered off,
washed several times with water and dried in vacuum.
Recrystallization from methanol yields 1.04 g of
N,N'-Bis(3,3-dimethylbutyl)-1,4-benzenedicarboxamide as white
powder.
Example 10: N,N'-Dipropyl-1,4-benzenedicarboxamide
##STR00016##
[0045] Triethylamine was stirred for 1 day over CaH.sub.2 and
finally distilled off. THF was refluxed for three days over
CaH.sub.2, distilled, refluxed for another three days over
potassium and finally distilled again. 2.67 mL of propylamine, 0.1
g of anhydrous LiCl, and 15 mL of triethylamine were dissolved in
100 mL of dry THF under inert atmosphere and cooled to 0.degree. C.
3.00 g of terephthaloyl chloride were added to the solution and
subsequently refluxed for 12 h. Then the solution was cooled to
room temperature and poured into water. The precipitate was
filtered off, washed several times with water. The crude product
was recrystallized from methanol yielding 1.5 g of
N,N'-Dipropyl-1,4-benzenedicarboxamide as yellowish needles.
[0046] Part B: Preparation of Polymer Resin Plaques with Bisamide
Nucleating Agents
[0047] The influence of bisamide nucleating agents on haze was
examined for three linear low density polyethylenes from The Dow
Chemical Company.
TABLE-US-00001 TABLE 1 LLDPE Properties Melt Index [2.16 kg,
Density 190.degree. C.] Name (g/cc) (g/10 min) DOWLEX 2045G 0.920 1
DOWLEX 2552E 0.920 25 TUFLIN HS-7028 0.918 1 NT7
[0048] DOWLEX 2045G is an ethylene-octene copolymer suitable for
blown film applications. DOWLEX 2552E is an ethylene-octene
copolymer suitable for injection molding and fiber applications.
DOWLEX HS7028 NT7 is an ethylene-hexene copolymer suitable for
blown film applications. Density was measured per ASTM D792, the
melt index per ASTM D1238.
[0049] Small-Scale Compounding and Injection Molding for Haze
Measurements
[0050] Blends of the polyethylene resins with the nucleators were
prepared in a laboratory co-rotating mini-twin-screw extruder
(Xplore from DSM, 15.0 ml volume) at 40 r.p.m. for 5 min at
220.degree. C., in a nitrogen blanket. First, a masterbatch of 2%
by weight of the nucleator was made in the polyethylene resin. This
masterbatch was diluted and re-compounded with neat polyethylene
resin to achieve the desired final concentration of the nucleator
in the polymer. The melt from the extruder was injected into a
circular mold kept at room temperature to produce plaques of 1.0 mm
thickness and 25.0 mm diameter.
[0051] Haze Measurements for Molded Samples
[0052] The haze of the injection-molded samples was determined at
room temperature with a Haze-Gard Plus.RTM. instrument (BYK Gardner
GmbH, Germany) according to ASTM standard D1003. A circular area on
the plaque samples, 18.0 mm in diameter, was illuminated by the
light beam; the recorded haze values are referred to as
"overall-area haze". In addition, haze values of a circular area
with 8.0 mm diameter on samples (those free of surface
irregularities) were recorded and are referred to as "small-area
haze". In order to eliminate the effect of surface scattering,
"bulk haze" measurements were conducted by filling a
50.0.times.45.0.times.2.5 mm cuvette, (AT-6180 from BYK Gardner
GmbH, Germany) with non-drying immersion oil (Cargille Series A
refractive index oil of n=1.5150.+-.0.0002) and inserting samples
therein. Haze values reported here correspond to the average of
values from five measurements.
[0053] Haze Data
[0054] Haze data for injection molded plaques of compounds made for
N,N'-bis(cyclohexylmethyl)-1,4-phenylene dicarboxamide (BCPCA) with
DOWLEX 2045G, DOWLEX 2552E and TUFLIN HS 7028 NT7 are given
below.
##STR00017##
TABLE-US-00002 TABLE 2 TUFLIN HS7028 NT7/BCPCA compositions
Overall-area Small-area Bulk Concentration haze haze haze (% w/w)
(%) (%) (%) 0 80.0 n/a 54.0 0.01 74.8 n/a 48.6 0.05 74.2 n/a 46.8
0.08 74.3 n/a 46.7 0.1 74.5 n/a 45.0 0.15 72.1 n/a 42.0 0.2 69.6
n/a 35.0 0.5 77.2 n/a 48.0
TABLE-US-00003 TABLE 3 DOWLEX 2045G/BCPCA compositions Overall-area
Small-area Bulk Concentration haze haze haze (% w/w) (%) (%) (%) 0
73.0 60.0 62.0 0.01 82.0 72.7 n/a 0.05 81.3 70.9 68.0 0.08 70.8
53.0 49.3 0.1 62.7 33.8 37.5 0.15 59.2 32.6 29.8 0.2 64.0 33.8 n/a
0.5 72.4 47.6 n/a
TABLE-US-00004 TABLE 4 DOWLEX 2552E/BCPCA compositions Overall-area
Small-area Bulk Concentration haze haze haze (% w/w) (%) (%) (%) 0
90.0 88.0 88.0 0.01 89.8 87.5 88.3 0.05 90.6 88.0 88.8 0.1 49.8
35.0 44.4 0.2 60.6 46.0 54.9 0.5 70.0 54.5 64.2 1 81.6 70.0
76.6
[0055] The following includes haze data for DOWLEX 2552E with
various nucleators.
##STR00018##
[0056] Table 5: Where substituent R is cyclohexyl for the table
below.
TABLE-US-00005 ##STR00019## Compound Compound Compound
Concentration A B C (% w/w) Overall-area haze (%) 0 90.0 90.0 90.0
0.002 89.8 89.0 89.6 0.005 89.7 89.9 90.4 0.01 89.7 90.3 90.7 0.025
91.0 91.0 93.0 0.05 92.3 91.9 83.7 0.1 78.2 80.0 82.0 0.2 78.2 75.4
87.0 0.5 79.7 73.3 94.0 1 91.8 84.9 98.0
[0057] Table 6: Where substituent R is cyclohexylmethyl for the
table below.
TABLE-US-00006 ##STR00020## Compound Compound Compound
Concentration A B C (% w/w) Overall-area haze (%) 0 90.0 90.0 90.0
0.002 88.0 89.4 88.7 0.005 88.6 89.5 88.9 0.01 89.8 89.9 89.4 0.025
89.9 90.9 90.4 0.05 90.6 91.8 78.7 0.1 49.8 92.1 65.6 0.2 60.6 92.7
78.0 0.5 70.0 92.4 97.4 1 81.6 97.0 100
[0058] Table 7: Where substituent R is cyclohexylethyl for the
table below.
TABLE-US-00007 ##STR00021## Compound Compound Compound
Concentration A B C (% w/w) Overall-area haze (%) 0 90.0 90.0 90.0
0.002 88.4 89.1 89.1 0 90.0 90.0 90.0 0.005 89.1 89.6 89.6 0.01
89.4 90.5 89.9 0.025 90.2 90.6 90.7 0.05 90.4 92.2 82.0 0.1 58.6
92.5 69.3 0.2 56.0 93.1 79.0 0.5 68.5 90.9 95.3 1 82.7 98.8 100
[0059] Table 8: Where substituent R is n-propyl for the table
below.
TABLE-US-00008 ##STR00022## Compound Compound Compound
Concentration A B C (% w/w) Overall-area haze (%) 0 90.0 90.0 90.0
0.002 88.6 89.6 89.0 0.005 89.0 90.7 89.7 0.01 90.0 90.9 90.5 0.025
90.8 91.4 92.2 0.05 76.2 92.2 77.4 0.1 81.8 92.5 80.7 0.2 85.5 91.7
81.6 0.5 91.2 86.9 89.6 1 94.1 89.0 94.3
[0060] Haze Data for DOWLEX 2552E with Compound A--and various
other R groups is provided in table 9 below.
TABLE-US-00009 TABLE 9 R group attached to Compound A Concentration
(% w/w) ##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027## 0 90.0 90.0 90.0 90.0 90.0 0.002 89.1 89.9 89.5 89.7
89.0 0.005 89.5 90.3 90.5 90.2 89.0 0.01 90.1 91.0 91.0 90.5 90.0
0.025 90.4 91.9 91.4 91.3 90.5 0.05 67.5 70.4 92.9 91.9 91.5 0.1
71.5 74.9 72.1 76.5 92.0 0.2 79.8 78.1 80.9 80.4 79.0 0.5 87.6 84.4
87.7 83.3 70.0 1 93.3 90.3 93.4 92.2 67.0 2 99.2 96.8 97.2 97.3
69.0
[0061] Part C: Polyethylene Film
[0062] Compounds were prepared with DOWLEX 2045G and BCPCA as
follows: the respective amounts of additive and base polymer were
put into a plastic bag and thoroughly mixed by turning the bag. The
powder mixtures were extruded on a twin screw extruder (Leistritz
ZSE MAXX, screw diameter=27 mm; screw 1/d ratio=48). Before
extruding the additive mixtures the extruder was cleaned with
standard LDPE and after that with 2 kg of the base polymer.
Processing parameters: Cylinder temperature: 170.degree. C. (all
heating zones), screw speed: 300-400 U/min, output: 25-30 kg/h. The
extruded strands were cooled in a water bath and cut with a
pelletizer. The obtained granulate was mixed in a mixer and packed
into PE plastic bags.
[0063] Exemplary monolayer polyethylene films comprising the DOWLEX
2045G and BCPCA compounds were produced on a monolayer blown film
line. Additional process parameters are provided in Table 10 below,
and haze results are provided in Table 11 below.
TABLE-US-00010 TABLE 10 Process Parameter Process Parameter Value
Screw diameter 30 mm Screw length 25 D Annular die size 60 mm Die
gap 1.2 mm Melt temperature 200.degree. C. Blow-up ratio 2.5 Film
thickness 50 .mu.m Output rate 5 kg/hr
[0064] Haze was measured based on the ASTM D1003-11 norm using
"Hazeguard Plus 4725" test equipment. Haze values given are the
average of 5 separate measurements. Samples were allowed to age for
minimum 40 hr prior to testing.
TABLE-US-00011 TABLE 11 Film Composition Average Haze % DOWLEX
2045G - reference 11.6 DOWLEX 2045G + 300 ppm bisamide 7.1 DOWLEX
2045G + 500 ppm bisamide 7.1 DOWLEX 2045G + 800 ppm bisamide
7.5
[0065] Part D: Comparison to Trisamide Clarifier
[0066] For polypropylene films, trisamide derivatives have
demonstrated improvements in optical properties, such as haze
reduction; however, they have not demonstrated the same level of
improvement in polyethylene films.
[0067] The following table depicts the haze reduction yielded by
tris(cyclohexylmethyl)-1,3,5-phenylene dicarboxamide (TCPCA) and
BCPCA when incorporated into a DOWLEX 2552E LLDPE plaque having a
thickness of 1 mm. As shown, the haze-reducing effect of a
trisamide was compared to a bisamide, which has the same R-group
moieties. Various haze measurements were conducted at increasing
concentrations up to 2% of the bisamide and trisamide, and the
minimum haze in the concentration range was provided below. As
shown, at 0.1% concentration, there is a haze reduction of over 40%
(90.0-49.8=40.2%).
TABLE-US-00012 TABLE 12 ##STR00028## ##STR00029## Concentration (%
w/w) Overall-area haze (%) 0 90.0 90.0 0.002 88.0 n/a 0.005 88.6
88.5 0.01 89.8 89.2 0.025 89.9 89.7 0.05 90.6 78.6 0.1 49.8 75.3
0.2 60.6 76.9 0.5 70.0 82.0 1 81.6 90.3 2 95.9 96.3
[0068] It is further noted that terms like "preferably,"
"generally," "commonly," and "typically" are not utilized herein to
limit the scope of the claimed invention or to imply that certain
features are critical, essential, or even important to the
structure or function of the claimed invention. Rather, these terms
are merely intended to highlight alternative or additional features
that may or may not be utilized in a particular embodiment of the
present disclosure.
[0069] It will be apparent that modifications and variations are
possible without departing from the scope of the disclosure defined
in the appended claims. More specifically, although some aspects of
the present disclosure are identified herein as preferred or
particularly advantageous, it is contemplated that the present
disclosure is not necessarily limited to these aspects.
* * * * *